Complexes containing phosporus and sulphur and methods of making same



United States Patent COMPLEXES CONTAINING PHOSPORUS AND :ULPHUR AND METHODS OF MAKING Peter A. Asseif, Cleveland, Thomas W. Mastin, Willoughby, and Alan Rhodes, Euclid, Ohio, assignors to The Lfubrizol Corporation, Wicklifie, Ohio, a corporation 0 Ohio N0 Drawing. 7 Application November 3, 1952, Serial No. 318,526

14 Claims. (Cl. 260-139) This invention relates to new compositions of matter, and more particularly pertains to novel organic salt complexes and novel methods of producing same.

It is now well known that when preparing a salt or soap of an organic acid, the mere use of an excess of neutralizing agent, which in the prior art has been in the form of an oxide, hydroxide, carbonate, etc. of a desired metal, results in a product which contains an amount of metal in excess of that theoretically required to replace the acidic hydrogens of the organic acid used as a starting material.

An object of the present invention is to provide novel salt complexes. Another object of the present invention is to provide new methods of producing novel salt complexes. A further object of the present invention is to provide novel salt complexes which are especially adapted for use in lubricants. Other objects or advantages of this invention will be apparent from the following explanation and description thereof.

Essentially the present invention comprises novel salt complexes formed with an oil-soluble acidic organic compound and/ or the salt thereof; a material which is hereinafter referred to as the promoter; salts or bases; and water.

Another aspect of the present invention involves salt complexes comprising an oil-soluble salt of an acidic organic compound having in complex formation therewith a salt or base, and said complex contains a higher salt fanning radical content than is heretofore known.

Still another aspect of the present invention is to treat the salt complexes mentioned above with a material which will possess acid characteristics in the process mass so as to adjust the alkalinity of the salt complex and/ or to partially or substantially completely recover the promoter in the ionizable form.

More particularly, the present invention is concerned with salt complexes prepared by the process which comprises preparing and mixing a mass in which, at 50 C., at least 50% of the components are in the liquid state, and in which mass the active components consist of:

A. A mixture of:

(i) At least one oil-soluble organic acid compound having at least 12 carbon atoms in the molecule selected from the class consisting of aliphatic and cyclic sulphur acids and the salts thereof; and

(ii) At least one oil-soluble organic acid compound having at least 12 carbon atoms in the molecule selected from the class consisting of the aliphatic and cyclic phosphorus acids and the salts thereof;

the ratio of equivalents of (i) to (ii) being from 0.10 to 10;

B. An organic compound selected from the class consisting of organic salt-forming compounds and the salts thereof, said organic compounds having- (i) An ionization constant in water of at least about 1X10 at about 25 C.;

ice

(ii) A water solubility at 50 C. of at least about 0.0005%; and (iii) In saturated aqueous solutions at about 25 C.

a pH of less than 7; the relative total amount of A and B used being in the range of from about one equivalent of the total amount of A to about 10 equivalents of B to about 10 equivalents of the total amount of A to about one equivalent of B;

C. A basically reacting metal compound;

(i) Which is water-soluble at a temperature of 50 C. to the extent of at least about 0.0003%;

(ii) In an amount such that there are present in the mass substantially more than 1 equivalent of metal, including the metal present in the remaining components, per equivalent of A plus B; and

D. Water, in an amount equal to at least about onetenth mole per mole of C;

maintaining the mass at a temperature and for a period of time sufficient to drive 01f substantially all free water and water of hydration which may be present, and form the organic metal complex.

Optionally, the above salt complex can be further modified by: Treating the mass with sufiicient amounts of a material which in the presence of the mass will form a material having a higther ionization constant than the organic salt-forming compound of component B, to liberate a substantial portion of said organic compound of component B.

If desired, the abve salt complexes prepared in accordance with the above optional step can then undergo treatment to remove from the mass so much of the organic salt-forming compound of component B as may have been formed by said step.

This application is a continuation-in-part of our copending application, Serial No. 216,101, filed March 16, 1951, and is a continuation-in-part also of our related copending applications, Serial No. 216,102 now U. S. Patent 2,617,049; Serial No. 216,103 new U. S. Patent 2,616,924; Serial No. 224,458 now U. S. Patent 2,695,910; Serial No. 263,961 now U. S. Patent 2,616,925; Serial No. 263,926 now U. S. Patent 2,616,911; Serial No. 263,963 now now U. S. Patent 2,616,904; Serial No. 276,461 now abandoned; Serial No. 276,462 now U. S. Patent 2,616,905; and Serial No. 318,521 now U. S. Patent 2,723,234.

In our aforesaid parent application Serial No. 216,101 there is disclosed the process of producing certain novel organic salt complexes and the novel products resulting from such processes. The present invention is a refinement within the teaching of said parent case in that it relates to the processes disclosed in said parent application producing novel complexes which have unexpectedly good characteristics and which complexes are characterized by the inclusion therein of the anions of both an oil-soluble high molecular weight organic sulphur acid and an oilsoluble high molecular weight organic acid of phosphorus.

The utilization of a plurality of different anions leads to advantages not only in the production of products which have properties which cannot be achieved by the use of a single anion but also makes possible the production of complexes in certain respects like those produced by the process of said parent case at considerable savings and cost. In the more specific embodiment of this invention the different anions referred to above are respectively derived from oil-soluble high molecular weight sulphonic acids and oil-soluble high molecular weight acids of pentavalent phosphorus. A list of various classes, subclasses, and specific examples of acid compounds from which may be derived the anions of the sulphur acids use- 1.11 in this process may be found in copending application,

Serial N 216,101 at page 15, line 33 thereof, through page 16, line 18.

From the broad class of available sulfuracid com- 1 pounds, it is preferred to employ the oil-soluble organic sulphonic acid compounds. Furthermore, of the available metal'salts of organic acids, the metal salts of groups I and II of the Mendeleef periodic table are preferred for V the reason that unexpectedly excellent results are obtained by the use thereof. These oil-soluble sulphonic acids, and the metal salts thereof can be represented by the following structural formulae:

In the above formulae M is a metal, preferably selected from groups I and 'II of the Mendeleef periodic table; T is acyclic nucleus either of the monoor poly-nuclear type including benZenoid or heterocyclic nuclei such as .ben-

zene, naphthalene, anthracene; phenanthrene, diphenylene, thianthrene, pheno'thioxine, diphenylene sulphide, di-' phenylene oxide, diphenyl oxide, diphenyl sulphide, diphenyl amine, etc; P; is an aliphatic group such as alkyl, alkenyLQalkoxy, alkoxy-alkyl, carboalkoxy-alkyl, or aralkyl'groups, x is at least 1, and Rx containing atotal of where the aliphatic group is alkyl, alkoxy, alkoxy-alkyl,

carboalkoxyalkyl, etc. Specific examples of R are cetylcyclohexyl, lauryl-cyclohexyl; ceryloxyethyl, and octadecenyl radicals, and radicals derived from petrolatum, saturated and unsaturated parafin wax, poly olefins, including poly-C3, C4, C5, C6, C7, C8, olefin hydrocarbons; The groupsT, R and R in the above formulaecan also contain other organic. or inorganic substituents in addition to' those enumerated above, such as for example,'hydroxy, mercapto, -halogen,.nitro, amino, nitr'aso, carboxy, ester,etc. j t

In Formula I above x, .yjz and 'b are at least one; whereas in Formula H, a, d, and c are atleast one.

The followingare specific examples of oil-soluble sulphonic acids coming within Formulae I and II above, and it is to be understood that such examples 'serv'eto also illustrate the metal salts of thesulphonic'acids. In other words, for everysulphonic acid,:it is intended that the metal salt thereof is also illustrated. i V The metal salts include the mono or polyvalent metals, suchas the light or heavy metals, or the metals-of group .1 having an atomic weight less than 40 and the metals .of group' H having an atomic weightless than 138, such as sodium, lithium, potassium, calcium, barium, strontium, magnesium, and other specific examples, are zinc, cadmium, mercury, lead, tin, iron, cobalt, copper, manganese, aluminum,chromium, nickel, etc. f

Illustrations of sulphonic acids contemplated for use as the sulphur acid in the process of this invention are contained in 'copending application, Serial No. 2l6,101 at page 13, line'9 thereof, through page 15, line 28.

It has been found that metal complexes of considerable utility may be produced when using as the starting material a mixture of at least two different sulfonic. acid' compounds.

Highly useful in this respect are mixtures containing (a)' at least one petroleum derived sulfonic acid compound, and (b) at least one alkyl-aroniatic sulfonic acid compound. Particularly preferred are mixtures of mahogany sulfonic acids or salts with alkyl-benzene sul-' fonic acids or salts. The ratio of equivalents of a/b is preferably between 0. 1 and 10. L a

The following examples illustrate a numberof specific ing salts of the sulfonic acids are also contemplated.

Mixture chemical No. Components equivaw 1 p {mahogany sulfonic acid di-isododecyl benzene sulfonic acid.

white oil sulfonic acid mahogany sulfonic acid. di-isododccylbeuzene sulfonic acidwhite oil sulfonic acid di-isododecyl benzene sulfonic a 4 {mahogany suifonic acid wax-substitutediphenol {mahogany suliouic acid wax-substituted naphthalene sulfonic acid {mahogany sulfonic acid -s wax-substituted benzene sulfonic acid pet'rolatum sulionic acid white oil sulfonic acid. mahogany sulfonic acid petrolatum 'sulionic'aeid mahogany sulfonic acidwhite 011 sulfonic acid {polybutene sulfonic acid {mahogany sulfonic {cieosyl diphenyl'ether s mahogany sulfonic acid {tri-capryl diphenyl ether sulfonic acidmahogany sulionic acid {bis-(diisobntyD-phenol sulfonic'aci White oil sulfonic acid {cetyl-chlorobenzene sulfonic acid 7 7 mahogany sultonic acid 16 {di-cetyl naphthalene sulfonic acid. 7

mahogany sulfonic acid {mahogany sulfonic acidwhite oil sulfonic acid di-lauryl diphenyl ether sulfonic aci di-isononyl benzene sulfonic acid. White oil disulfonic acid 18 {di-isooctadecyl benzene sulfonic aci petroleum naphthene sulfonic acids 19 mahogany sulfonic acid;

polybutcne-substituted benzens sulfo {di-keryl benzencsulionie acid mahogany 'sulfonic acid.

{fuel oil substituted benzene sulfonic acid. [mahogany sultonic acid 22 {stearyl naphthalene sulfonic acid T white oil sull'om'c aci l 3 {wax-substituted phenothioxinc sulfonic aci mahogany sullonic acidi wer s r z rmr r r'rr for example, phosphorus, phosphoric, thiophosphoric, thiophosphorous, phosphinic, phosphonic,thiophosphinic, V

thiophosphonicp'etc; acids.

Among the useful phosphorus acids are those represented by the following formulae:

a l l wherein X and X are either oxygen or sulfur and R 'andjR are each either the same or diiferent organic radicals or hydrogen, and wherein at least one is' an organic radical and at least one R'is hydrogen and Wherein at least one R is an organic radical and at least one' inorganic thio-acids of phosphorus, more particularly the lents organic thiophosphoric acids and the organic thiophos- .phorous acids. The organic radicals R and R can be aliphatic, cycloaliphatic, aromatic, aliphaticand cycloaliphatic-substituted aromatic, etc. The organic radicals R and R preferably contain a total of at least about 12 carbon atoms in each of the above acid types I and 11. Examples of such acids are di-lauryl phosphoric acid, 'di-wax phosphoric acid, dicapryl dithiosphosphoric acids, di-(methyl-cyclohexyl) dithiophosphoric acids, dilauryl dithiophosphoric acids, dicapryl dithiophosphorous acids, di-(methyl-cyclohexyl) dithiophosphorous acids, lauryl monothiophosphoric acids, di-(butyl-phenyl) dithiophosphoric acids, and mixtures of two or more of the foregoing acids. Additional examples of phosphorus acids of types I and II are given herein below. For each acid, the corresponding metallic salts of the light and heavy metals; e. g., sodium, lithium, potassium, calcium, barium, strontium, magnesium, zinc, copper, tin, lead, and aluminum, etc., are also contemplated. Particularly preferred are the alkali and alkaline earth metal salts, with a special preference for the barium salts.

Phosphoric acids:

' Dihexyl phosphoric acid Dioctyl phosphoric acid Didecyl phosphoric acid Diundecyl phosphoric acid Didodecyl phosphoric acid Dioctadecyl phosphoric acid Dihexenyl phosphoric acid Dioctenyl thiophosphoric acid Didecenyl phosphoric acid Dioctadecenyl phosphoric acid Dicyclopentyl phosphoric acid Dicyclohexyl phosphoric acid Di-(methylcyclohexyl) phosphoric acid Dicyclopentenyl phosphoric acid Dicyclohexenyl phosphoric acid Di-(methyl-cyclohexenyl) phosphoric acid Di-(phenylbutyl) phosphoric acid Di-(naphthylethyl) phosphoric acid Di-(chlorophenyloctyl) phosphoric acid Di-(propylphenyl) phosphoric acid Di-(methyl-naphthyl) phosphoric acid Methyl decyl phosphoric acid Ethyl dodecyl phosphoric acid Ethyl methylcyclohexyl phosphoric acid Monoand di-esters of thiophosphoric acid, e. g.:

0,0-di-n-hexyl thiolthioncphosphate 0,0,di-n-hexyl thionophosphate 0,0-di-(4-methyl-sec-amyl) thiolthionophosphate O,S-di-n-heptyl dithiolthionophosphate 0,0-di-(2-ethyl-hexyl) thiolthionophosphate 0,0-di-capryl thiolthionophosphate 0,0-di-(2,4,4-trimethyl-amyl) thiolthionophosphate O,S-di-n-nonyl dithiolphosphate 0,0-di(3,5,5-trimethyl-hexyl) thiolthionophosphate 0,0-di-n-decyl thiolthionophosphate S,S-di-n-undecyl dithiolphosphate 0,0-di-lauryl thiolthionophosphate S-cetyl dithiolphosphate 0,0-di-cetyl thiolthionophosphate Thiolthionophosphates of the general formula (CnH2n10)2PSSH, where n is a number of from 20 to 50, e. g.:

0,0-di-(parafiin wax) thiolthionophosphates 0,0-di-myricyl thiolthionophosphate 0,0-di-carnaubyl thiolthionophosphate 0,0-di-(tert-amyl-phenyl) thiolthionophosphates 0,0-bis-(diisobutyl-phenyl) flaiolthionophosphates 0,0-di-(decyl-phenyl) thionophosphates O-cetyl-phenyl-O-naphthyl thioltbionophosphates 0,0-di-(methyl-cyclohexyl) thiolthionophosphates 0,0-di-(amyl-cyclohexyl) thiolthionophosphates Pentacosyl-cyclohexyl tetrathiophosphates O,S-di-(heptyl-cyclohexyl) dithiolthionophosphate Particularly preferred are the di-(organo) dithiophosphoric acids, e. g.:

Dihexyl dithiophosphoric acid Diheptyl dithiophosphoric acid Dioctyl dithiophosphoric acid Dinonyl dithiophosphoric acid Didecyl dithiophosphoric acid Didodecyl dithiophosphoric acid Ditetradecyl dithiophosphoric acid Dihexadecyl dithiophosphoric acid Dioctadecyl dithiophosphoric acid Di-(parafiin wax) dithiophosphoric acid Dieicosyl dithiophosphoric acid Dipentenyl dithiophosphoric acid Dioctenyl dithiophosphoric acid Didecenyl dithiophosphoric acid Dihexadccenyl dithiophosphoric acid Di-(methyl-benzyl) dithiophosphoric acid Di-(octylbenzyl) dithiophosphoric acid Di-(phenyloct-adecyl) dithiophosphoric acid Di-(xenylhexyl) dithiophosphoric acid Di-(phenoxyoctyl) dithiophosphoric acid Di-(butoxy-ethyl) dithiophosphoric acid Bis-(3,5-dichloro-n-octyl) dithiophosphoric acid Bis-(2,6-dibromo-n-decyl) dithiophosphoric acid Dicyclopentyl dithiophosphoric acid Bis-(dimethylcyclopentyl) dithiophosphoric acid Dicyclchexyl dithiophosphoric acid Di-(methyl-cyclohexyl) dithiophosphoric acid Di-(isopropylcyclohexyl) dithiophosphoric acid Bis-(diisobutylcyclohexyl) dithiophosphoric acid Dinaphthenyl dithiophosphoric acid Di-(hydroabietyl) dithiophosphoric acid Dicyclopentenyl dithiophosphoric acid Di-(methylcyclohexenyl) dithiophosphoric acid Diabeityl dithiophosphoric acid Di-(tert-amyl-phenyl) dithiophosphoric acid Di-(2,4-di-tert-amyl-phenyl) dithiophosphoric acid Di-(paratfin wax-phenyl) dithiophosphoric acid Di-(lauroxyphenyl) dithiophosphoric acid Di-(caprylxenyl) dithiophosphoric acid Methyl octadecyl dithiophosphoric acid Partial esters of pyrophosphoric acid:

Mono-, di-, and tri-eicosyl pyrophosphates Mono-, di-, and tri-(ceryl-phenyl) pyrophosphate Mono-, di-, and tri-(cetyl-cyclohexyl) pyrophosphates Partial esters of pyrophosphorous acid:

Mono-, di-, and tri-octadecyl pyrophosphites Mono-, di-, and tri-(myricyl-phenyl) pyrophosphites Mono-, di-, and tri-(cetyl-cyclopentyl) pyrophosphites Mono-, dig and tri-ceryl'S-pyro thiophosphites .Mono-, .di-, "and tri-(docosyl-phenyl) jO-pyrotetrathiolph osphites Mono di-fan'd tri-(lauryl-cyclohexyl) pywpfintar thiophosphites i V 7 Partial esters of thiopolyphosphoric acids, e. g.:

Mono-, di-, tri-, and tetra-ceryl decathiotriphosphates Mono-, di-, tri-, tetra-, and penta-(dicapryl-phenyl) tetrathionotetraphosphates Mono di-, tri-, tetra-, penta-, and hexahydroabietyl pentathionopentaphosphates Partial esters of thiopolyphosphorous acids, e. g.:

Mono-, di-, tri-, and tetra-myricyl'heptathiotriphosphites Mono-, di,-'tri-, tetra, and penta-(lauryl-phenyl) trithiotetraphosphites Mono-, di-, tri-, tetra, penta-, and hexa(petroleum naphthenyl) tetrathiopentaphosphites Also useful in the production of the metal complexes of the present invention are the organic phosphorus acids which contain at least one carbon-to-phosphorus bond; i. e., those'acids of the general formula:

III. x.

wherein X 'and'X are oxygen or sulfur, R. is an organic radical bonded to phosphorus through a carbon atom, nis-1'or2', aiidmisOor 1. 7

Other carbon-to-phosphorus bonded organic acids of phosphorus useful in the production of our metal complexes, but whose exact structures'have not yet been ascertained, may be prepared by the treatment of aliphatic and/ or aromatic hydrocarbons with at least one sulfurizing and phosphorizing reagent such as PSCla, P255, P457, P285 plus sulfur, RG13 plus sulfur, and the like, and optionallyf treating thereafter with a hydrolyzing agent such as wateiysteam, and/or metallic base. The preparation of such materials is disclosed in U. S. Patents Nos;

2,316,091; 2,316,078; 2,316,079; 2,316,080; 2,316,081; 2,316,082; 2,316,083; 2,316,084; and 2,367,468.

Specific examples of organic acids of phosphorus containing at least one carbon-to-phosphorus linkage are 'givenhereinbelow. These examples include both acids of known structures; i. e.,those of type III above, and acids whose structures have not been clearly established; e. g., the types of materials discussed in the previous paragraph.

For each acid, the corresponding metallic salts of the light and heavy metals; e. g., sodium, lithium, potassium,

calcium, barium, strontium,.magnesium, zinc, copper, tin, I lead, and aluminum, etc., are also contemplated. 'Par- 'ticularly preferred are the alkali and alkaline earth metal salts, with a special preference for the barium salts. V

Acids of the general formula RPX(X'H)2, wherein R is an organic radical bonded to phosphorus through a carbon atom and X and X are 0 or S for example:

Phosphonic acids, e. g:

N-Hexyl phosphonic acid N-Octyl phosphonic acid Capryl phosphonic acid Decyl-2-phosphonic acid Lauryl phosphonic acid Cetyl phosphonic acid Chloro-cetyl phosphonic acid Parafiin wax phosphonic acid Cyclohexyl phosphonic acid Methyl-cyclohexyl phosphonic acid Ethyl-chlorocyclohexyl phosphonic acid Petroleum naphthenyl'phosphom'c' acid" Tertiary-amyl-phenyl phosphonic acid Djisobutyl-phenyl phosphonicacid a Tertiary-butyl-nitrophenyl phosphonic acid aroma;

' 'Wax-phenyl phosphonic acid A-lpha-inethyl-naphthyl phosphonic acid Cetyl-bromophenylphosphonic acid Phosphonic acids derived from po lecular weight range 400'10,000

Thiophosphonic acids, e..g.: ,7

i 'N-H'exyl thionophosphonic acid N-Heptyl thiolth i'o nophosphonic acid Lauryl tr'ithiophosphonic acid Par'afiin wax thionophosphonic acid Diisobutyl-cyclohexyl thiolphosphonic acid 7 Tertiary-amyl-phenyl thionophosphonic acid Diisobutyl-phenyl thionophos phoniclacid Tertiary-butyl-nitrophenyl thionophosphonic acid a Alpha-methyl-naphthyl' thionophosphonic acid Thiophosphonic acids derived from molecular weight range 400-10,000

Acids of the general formula V V Pxzx'n wherein R1 and R2 are the same or dilferent organic radi: cals bondedto phosphorus through a carbon atom and V X and X are 0 or S, for example:

Phosphinic acids, e. g.:

Di-n-hexyl phosphinic acid Di-(Z-ethyl-hexyl) phosphinic acid Di-n-undecyl phosphinic acid Di-(paraflin' wax) phosphinic acid Phosphinic acids derived from polybutenes of molecular weight range 400-10,00 0

Di-(amyl-cyclohexyl) phosphinic acid Di-(cetyl-cyclopentyl) phosphinic acid Di-(tertiary-amyl-phenyl) phosphinic acid Di-(n-butyl-nitrophenyl) phosphinic acid Di-(chloro-phenyl) phosphinic acid I Di-(parafiin-wax-phenyl) phosphinic acid Acids of the general formula RP(XH )2 (may exist as wherein R is an organic radical bonded to phosphorus through a carbon atom and X, is O'or S, "for example:

Phosphonous acids, e. g.:

n- Hexyl phosphonous acid Iso-octyl phosphonous acid Paraflin wax phosphonous acid Phosphonous acids derived from polybutenes in the inolecular weight range of 400 to'1 0,00 0 Lauryl' cyclohexyl phosphonous acid Petroleum naphthenyl phosphonous acid Hydroabietyl phosphonous acid Tertiary-amyl-phenyl phosphonous acid Capryl-nitronaphthyl phosphonous acid Thiophosphonous acids, e. g.:

3-hexyl-thiophosphonous acid Diisobutyl dithiophosphonous acid Monoand di-thio phosphonous acids derived frorn (1) Parafiin wax (2) Polybutenes in the molecular weight range of 400 to 10,000 Cetyl-cyclohexyl thiophosphonous acid n-Hexyl-phenyl thiophosphonous acid Tertiary-butyl-chlorophenyl dithiophosphonous acid Ethyl-naphtnyl dithiophosphonous acid Acids f the general formula PXH (may exist as P where R1 and R2 are the same or different organic radicals bonded to phosphorous through a carbon atom and X is O or S, for example:

Phosphinous acids, e. g.:

Di-n-hexyl phosphinous acid n-Hexyl capryl phosphinous acid Di-eicosyl phosphinous acid Di- (lauryl-cyclohexyl) phosphinous acid Di-(isopropyl-phenyl) phosphinous acid Di-(butyl-nitrophenyl) phosphinous acid Thiophosphinous acids, e. g.:

Di-lauryl thiophosphinous acid Di-cetyl thiophosphinous acid Lauryl chlorononyl thiophosphinous acid Di-(petroleum naphthenyl) thiophosphinous acid Di-(ethyl-cyclohexyl) thiophosphinous acid Di-(decyl nitrophenyl) thiophosphinous acid Di-(ethyl chloronaphthyl) thiophosphinous acid Phosphorous acids of undetermined structure containing at least one carbon-to-phosphorous linkage; for example, the acids prepared by reacting 0.5 to 20 parts by weight of at least one of the organic materials listed under A with one part by weight of at least one of the inorganic phosphorizing or phosphosulfurizing agents listed under B for a period of from 2 to 20 hours at 120 to 300 C., then hydrolyzing with hot water, steam, or caustic:

Ethyl-benzene Di-propyl benzenes Butyl benzenes Diisobutyl-benzenes Cetyl-benzenes Eicosyl-benzenes Paraffin wax substituted 1. Benzene 2. Naphthalene 3. Anthracene 4. Phenanthrene Diphenyl ether Butyl diphenyl ether Alpha-methyl-naphthalene Isobutyl-naphthalene Isononyl-naphthalene Aromatic fractions from petroleum obtained by solvent-extraction processes Thianthrene Butyl-phenothiazine PCls PCls plus sulfur PC13 plus oxygen or air PSCls POCls P253 P235 Pass P457 HPOs H4P2Os Phs Elemental phosphorus Elemental phosphorus plus oxygen or air THE PROMOTER Compounds which may be employed as promoters in the hereindescribed process are described in copending application, Serial No. 216,101 at page 23, line 19 thereof, through page 35, line 6.

SALTS AND BASES (THE BASING MATERIAL) Salts and bases which may be employed as the basing material are illustrated by the list of examples contained in copending application, Serial No. 216,101 at page 38, line 23 through page 39, line 34; page 39, line 40 through page 43, line 24; and page 43, line 57 through page 47, line 29.

The formation of the salt complex is accomplished with water or an alcohol or mixtures of both. The water is present as a result of addition to the mixture, or is liberated from compounds incorporated into the mixture as a result of being subjected to processing temperatures. It is preferred to employ water which is added to the mixture.

The alcohol employed can be either monohydric or polyhydric, and should preferably be at least about 5% water soluble at 15 C. Examples of monohydric alcohols are methanol, ethanol, propanol-l, propanol-Z, butanol-l, butanol-Z, isobutyl alcohol, t-butyl alcohol, pentanol-3, etc.; and examples of polydric alcohols are ethylene glycol, propylene glycol, butylene glycol, amlylene glycol, hexylene glycol, pentaerythritol, etc.

Water and alcohol can be used together in efiecting the formation of the salt complex. Ordinarily mixtures of the same inany relative proportion are useful, however it is preferred to employ mixtures containing at least 60% Water.

THE ACIDIC MATERIAL as a description of the processing conditions as they per- 1i r tain to the use of alkaline earth metal reactants, and; the

relative. amounts of reactants to be used in theprocess, reference maybe had to U. S. Patent 2,616,924- column 34 line 28 thereof through column 35 line 18, and column 35 line 37 through column 44 line 20. In thisgconnection 7 while the description or" the above-identified patent refers to reactants containing alkaline earth metals, for. the purposes of the hereindescribed process it is intended that such descriptions are applicable to metal complexes broadly. V V V V The following examples give the preparationof'a plurality ,of products which range in metal. content from about that of the normal salt up to many times that amount.

We have found that sulphate ash and/ or metal content values, and the metal ratio values calculated therefrom,

are one means for characterising certain of the salt com;

plexes. 'As the description or" the invention proceeds, it will become apparent that the neutralization number of a salt complex is in certain instances an unreliable index of the amount of excess metal in such complex, since it is greatly affected by the type of inorganic alkaline. earth over a period of about 1% hours.

compound employed and can be varied within widelimits without significantly changing the metal content of the product by treatment of the mass with air, CO2, and the like.

The above is not to be construed as a statement that the neutralization number is not an important property of a a salt complex. For some uses, for example in lubricants,

it is advantageous in certain instances to employ a. salt complex of a substantially neutral character, whereas in other instances a salt complex of high alkalinity has been found to produce the desired results.

. V 7 Example 1 1886 grams of isononyl-substituted phenol were admixed with 2760 grams of a 4 0% oil'solution of barium petroleum sulfonate (10.0% sulfate ash content) and such mixture reacted-with 295'grams of P285 for 2' hours at ;l00110 C. to prepare di-(isononyhsubstituted phenyl) sulfonate and barium di-(isononyl-substituted phenyl) dithio-phosphate, '121 grams of diisobutylphen'ol, 564,

grams of low-viscosity mineral oil, and 500 ml. ofrwater were stirred about 60C. and 265 grams of'barium oxide added. The mass was heated for one hour at 100110 Cfandthen raised to 150 C. where it was treatedwith a current of CO2 until a sample showed a substantially neutral titre. In order to remove substantially all'ofjany 'water. remaining, the mass was heated for anad'ditional hour at ISO-160 C.

Filtration of he mass yielded 1452 grams of a brown free-flowing, oilsoluble liquid sulfonate dithiophosphate complex which was found to have the following analyses:

726 grams of the filtered mixture of barium petroleum C. for one hour. V

Thereafter, the bulk-ofthe water was removed by heating to; 150 C. over a period of approximately 3.5 'hours.

150 C. until a substantially neutral titre was observed,

. I2 3408 grams of polymerized isobutylene having an average molecular weight of about 750 wereintroduced into a reaction'vessel equippedwith stirrer, thermometer, and reflux condenser. While-the mass was stirred at about 210 C., an intimate mixture of 672 grams of powdered P255 and 84 grams of sulfur flowers wasv added. slowly been completed, the reaction mass was maintained at 205- 215 C. for an. additional 2% hour period.

Thereafter the whole was allowed to cool to about 100. p C. and 1082 grams of Ba(OH)2.8l-I2O purity). were added over a two-hourperiod at -115 C. (there is a tendency for the mass, to foam during this step of the process, which tendency can be controlled by adding the barium hydrate in small increments). 2556 grams of a low-viscosity, solvent-extracted, Mid-Continent oil were added and the whole was stirred for about '1 hour at C., then substantially all of any water present was removed by heating to. 160 C; and maintaining the process mass at that temperature for about 0.5 hour The crude material was purified. by filtration, yielding 5300gra1ns of a viscous, red-brown, oil-soluble liquid.

(b) 1110 grams of a 40% oil solution of barium petroleum sulfonate (10% sulfate ash content) were mixed with 1610 grams ofthe barium salt produced under (a) above (ratio of equivalents of sulfona-te to salt of high molecular weight phosphorus acid is 1.0). 248' grams of diisobutyl-phenol (ratio of'combined equivalents of sulfonate andsalt ofrhigh molecular weight phosphorus acid to'diisobutyl-phenol is 1.66) and 600 m1. of water were added, and the whole was stirred at about 70 C. 603 grams of BaO were. added" slowly as the temperature was gradually raised to about 105 C. After all of the BaO had been added, the mass was maintained at 105 CO2 was passed; through the process mass at then the CO2. treatment was discontinued and the temperature of mass maintained for onehour at 155 C. to remove substatniallyall of any water still present.

The mass was filtered, yieldingas filtrate 3103 grams of V a clear, oil-soluble, brown liquid having the following analyses;

Basic No; 10.2 Percent barium 16.6 Percent sulfate ash (calculated) 2&2 Percent phosphorus c 0.67 Percent sulphur 1.15

Metal ratio 4.38

. mass was raised to 105 C. and maintained atthat tem- Basic No 13:2. Percent barium 717-.3- Percent sulfate ash (calculated) 29.4. Percent phosphorus 0.52 Percent sulfur 1.76 Metal ratio 4,39

' Example 2 we a i t lt f a h h mo ecu ar :W ishtnhQe Q -efi of nde mined: t tur .w s: reparer eis lsu ee name-5' Example 3 1110 grams. of -40% oil solutionof barium petroleum sulfonate. 10% sulfateash content) were'mixed with 1110 grams of the barium salt described'inExample 2,

part a (ratio of equivalents of sulfonate to salt" of high molecular weight phosphorus acid is 1.5). '208 grams of diisobutyl-phenol (ratio of combined equivalents of sulfonate and salt ofhigh! molecular weight phosphorus acid to diisobutyl-phenol is 1.66) and 300 ml; of water were added, and the whole was stirred at about 70 C. 504 grams of BaO were then introduced and thep'rocess perature for about} hour.

Thereafter, the bulk of the waterwasremoved by heating to 150 C; over a period of about 2 hours. CO2

was passed through the'process mass,at,-.150 C. until a substantially neutral titre was obtained, then the CO2 treatment was discontinuedzand themass was maintained at 150 C. for about /2 hour to removesubstanti-ally all of any water still present. 31 grams of nonylalcoholwere added and the mass was 'fter the addition had filtered, .yielding as filtrate-26.12

grams of a brown, oil-soluble liquid having the following analyses:

Example 4 odor. The following properties were determined:

Basic No s 87.1 Percent barium 28.6 Percent sulphate ash (calculated from metal content) 48.8 Metal ratio 5.22

Example 5 172 grams of di-(n-hexyl) dithiophosphoric acid, 500 grams of petroleum sulphonic acid and 98 grams of paratertiary-butyl phenol (ratio of equivalents of oil soluble acids to para-tertiary-butyl phenol is 1.52) were mixed together. To this mixture was added a slurry of 387 grams of BaO and 1,080 cc. of water. The mixture was heated at 100 C. for one hour, and then the temperature was raised to 150 C. and held at that level for one hour. The product was a highly viscous liquid, brown in color, and contained a slight odor. The following properties of the product were determined:

Basic No 121 Percent barium 30.05

Sulphate ash (calculated from metal content) 51.0

Metal ratio 5.36

I Example 6 Basic No 30 Percent sulphate ash 32.3 Metal ratio 3.86

Example 7 A mixture of 497 grams of di-n-hexyl dithiophosphoric acid, 1465 grams of petroleum sulfonic acid, 1160 grams of barium oxide, 297 grams of p-tert-butyl phenol (ratio of equivalents 1.52) and 3100 ml. of Water was heated at reflux temperature for one hour, then at 150 C. for one hour. The reaction mixture was cooled to 110 C., treated with a stream of carbon dioxide at this temperature until the mixture was neutral, then treated with 14 Hyflo and filtered. The filtrate weighed 3660 grams and had the following properties:

Basic No. 14.0 Percent sulphate ash 49.7 Metal ratio 5.07

Example 8 Acid No. 1.71 Percent sulphate ash 47.7 Metal ratio 5.35

Example 9 260 grams (0.75 equivalent) of di-n-hexyl ditbiophosphoric acid, 717 grams (0.75 equivalent) of a 60% oil solution of petroleum sulfonic acid, 88 grams (0.99 equivalent) of l-nitro propane, 580 grams (7.6 equivalents) of barium oxide, 760 grams of low viscosity mineral oil, 1% liters of water were refluxed for one hour at 90 to C. Thereafter the process mass was elevated to 150 C. and held for one hour. After the whole had cooled to room temperature, CO2 was blown through the complex until it showed a substantially neutral titre. It was then filtered yielding a somewhat viscous light brown oil-soluble liquid having the following analysis:

Metal ratio A 0 Example 10 To a mixture of 782 grams of di(keryl-phenyl) dithiophosphinic acid, 1535 grams of a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content, 7.6%), 314 grams of isononyl phenol (ratio of equivalents, 1.70) and 1970 grams of water, was added 740 grams of barium oxide and this mixture was heated at reflux temperature for one hour. The mixture then was heated to 150 C. and held at this temperature for one hour whereupon it was allowed to cool and was treated at 50-60 C. with a stream of carbon dioxide until the mixture was substantially neutral. It was reheated to C., treated with Hyflo and filtered. The filtrate had the following physical properties:

Acid No. 1.26 Percent sulphate ash 31.6 Metal ratio 3.87

Example 11 mass had cooled to 70 C. it was blown with carbon dioxide for one hour at 40 to 70 C. Filtration of the process mass yielded a viscous oil-soluble dark brown liquid having the following analysis:

Percent sulphur 4.19 Percent phosphorus 1.29 Percent barium 24.6 Percent sulphate ash (calculated) 43.5 Acid No. 1.35 Metal ratio 5.42

q C. and heldtthere for a period ofone. hour. On filtration'the process. mass yielded an oily brown oil-soluble liquid having the following propertisrz; V v 7 Percent sulphur 3.23

Percent phosphor'u's" l 1.09

Percent barium i l i i 15.3

Percent sulphate ash (calculated) 26.0

Basic No. 41.8

Metal ratio 3.52

Example 13' To a stirred mixture of 765 gramsof a; 30 by. Weight oil solution of barium petroleum sulfonate .(sulphateash content, 7.6%),193 grams of. di-n-hexyl. thiophosphoric acid, 99, grams of p-tert-butyl phenol (ratio of equivalents,

' 1.52) 'and' 930 grams. ofwater, wasadded 348' grams of barium. oxide (at a temperature 0580 C.).. This mixture was stirred for one hour at 100 (3., then. for one hour at 150 C. The mixture was cooled to 60 C. and treated for ten hours with. a stream, of carbon diox-ide. Hyflo was added to the product and it was filtered; the filtrate had the. following. physical. properties 7 Basic No 5.43 Percent" sulphate ash; f30.5

Metal ratio 2.38

i V p Ex mple. 1.4 A mixture of. 765 grams. of, a 30% by weight oil solution of barium petroleum sulphonate (sulphate ash content-,.7.6% 350; grams: of di.-(paratfin wax.) phosphoric acid, 99fgramsof, p-tert-butyl phenol. (ratio-of: equivalents,.

1.52); 348- grams of barium oxide, 900 grams of water and 25: gramsofmethylcyclohexanol was heated at-100 C. for one hour, then heated to 150 C. and treated with a stream of carbon dioxide for 1.5 hours at 150- 180 C. The product mixture was treated with 'H y'fio and filtered, the filtratev having the following physicalproperties: J

Basic No; I Percent sulphate ash-.' 32.5, Metal ratio r 3.39

Exantple 15 7 A mixture of 765 "grams of a 30% by weight-oil solution of barium petroleum sulphonate (sulphate'ashconjtent, 7.6%), 232 grams of mono-(parafiin' wax) phosphorous acid, 156 grams of isononyl phenol (ratio of equivalents, 1.52), 344;grams of .barium oxide and.900 grams of water was heated at 100 C. for one-hour, then heated to 150 C. and treated at tlrisitemperature. with a stream ofcarbon dioxidefor one hour. Hyflowas To a stirred mixtnreof 416 grams of di(keryl -phenyl) dithiophosphinic, acid,.. 1535. grams. ofa: 30% by weight i ll. of, barium v.ygz'etroleum. sulphonate (sulphate ash content, 7.6% .3 16 .grams. of. isononyl phenol' (ratio of eq l n L52). and l 8:60grams o'f-water was-added in smallportions ,627; grams.. of.barium. oxide." The-mix ar a a gepiygd b abstraction of from kerosene.

ture was heated at refluxtemperature for onehour, then at 150 C. for one hour. The product was cooled'and treated at -60 C. with a stream of carbon' dioxide until it was substantially neutral. 7 The; mixture; was treated with Hyflo and filteredi The filtrate had the following physical properties:

Percent sulphate ash"2;;lnaaaeafi nee m 32.1 7

Metal ratio 3.57

Example 17 V A high molecular weight or'gano-phosphorus acid of. V undetermined structure was first prepared in the followingjmanne'r: V a 7 1312 grams (10.41 moles) of iso'noneneand 578 grams (2.6 moles) of P285 were reacted together for about.4 hours at 130 C; The'fre'sulting reaction mixture was added slowly to a hot (100' C'.) solution of 1574' grams (39.3 moles) of NaOH in 4.7 lite'rs'of Water and the Whole was stirred for 5 hours at 100 C. Ice was then added to dilute and cool the contents and then con'centrated hydrochloric acid was added slbwlyuntil the mixture was slightly acidic. extracted with a volume of beniene, washediwith water, dried over anhydrous MgSOlr and filtered Removal of benzene from the filtrate by heating under reduced pressure, yielded the desiredorgano-phosphorus acid. It was.

a viscous, red-brown liquid containing 18.3% sulfur and 6.8% phosphorus. Analysis. also indicated that it contained carbon to phosphorus'linkages. V

167 grams (0.355 equivalent) of the aboveorganophosphorus. acid, 1110 grams: (1.0'eq'uivalent) of a40% oil solution of barium petroleum sulfonate (10.0%,sulfateash content), 168 grams (0.817 equivalent) of diisobutyl-phenol (ratio of equivalents of combined sulfonate and organo-phosphorus acid to diisobutyl-phenol is 1.66), 436 grams (5.7 equivalents) of BaO, and 288 ml. of'water. were: mixed and stirred at 90100 C(for one? hour. Thereafter the process mass Was heated to" 150 C. to. remove the bulk .ofthe water. After most of the Water had been removed, a current. of COz was admitted until a titre of the mass indicated that it was Percent phosphorus 0.52 Percent barium q p 21.2 Percent sulfate ash (calculated). Metal ratio r 4.52

substantially neutral. (about 2 hoursrequired). After" heatingthe process massfon an additional hour at 150 C. it was. filtered; The filtered: product was" a clear, viscous, dark-brown, oil-soluble liquid having-the following' analysis:

Percent sulfur 2.53 7

Basic No.

i 7 Example 18 l409'grarns (4176 moles) of' eicosy l alcoholand 264 grams (1.18m0les) of P2'S5 were r'eacted .for 4110mm 96 C. to prepare di-eicosyl'dithiophosphate. The latter compound was blown, with' steam for 1.5 hours at 100120 C. to remove one of the sulfur'atoms'in the.

molecule, yielding di-eic osyl rnonothiophosphate. 325' grams (0.548 equivalent) of dieicosyl monothiophosphat'e, 1110 grams (l equivalent) of a 40% oil solution of barium petroleum sulfonate (10% sulfate ash, content), 192 grams (0.93 equivalent) of diisobutyle phenol (ratio of equivalentsof combinedthiophosphate and sulfonate. to' diisobutyl phenol is 1.66 a 508 rams 6.64 equivalents) of'BaO, and-326 ml. of water were" stirred. and heated for one hour at 100 C. Thereafter the'tprocessmass was heatedt0i150 C. and blown with a' current of COz' until a 'substantially'neutral titre'was The mass "wasthen obtained (about 2;hou'rs required).

heated anedditional hourat C. to removersubstane tially all of any water present and filtered. The filtered The organic layer was then 17 product was a clear, dark-brown, viscous oil-soluble liquid having the following analyses:

Percent sulfur 2.0

Percent phosphorus 0.55

Percent barium 21.3

Percent sulfate ash (calculated) 36.2

Metal ratio 4.52

Basic No. 7 9.1 Example 19 2848 grams of hydroabietyl alcohol were reacted with 484 grams of P285 for 4 hours at 96 C. to prepare dihydroabietyl dithiophosphate. The latter compound was treated with steam for 1.5 hours at 100-120" C. to remove one of the sulfur atoms in the molecule, yielding dihydroabietyl monothiophosphate.

299 grams (0.4 equivalent) of di-hydroabietyl monothiophosphate, 1110 grams of a 40% oil solution of a mixture equal molecular parts of barium petroleum sulfonate and barium di-isododecyl benzene sulfonate, 174 grams (0.843 equivalent) of diisobutyl-phenol (ratio of equivalents of combined phosphorus acid and sulfonates to diisobutyl-phenol is 1.66), 493 grams of BaO, and 317 ml. of water were stirred one hour at 100 C. Thereafter the process mass was heated to 150 C. and blown with a current of CO2 until a substantially neutral titre was obtained (about 1.5 hours required). The mass was then heated for an additional hour at 15 C. and filtered. The filtered product was a viscous, dark-brown, oilsoluble liquid which became tacky on cooling to room temperature. It analyzed as follows:

Percent sulfur 2,1 Percent phosphorus 0.60 Percent barium 20.0 Percent sulfate ash (calculated) 34.0 Basic No. 8.5 Metal ratio 4.45

Example 20 A high molecular weight organo-phosphorus acid of indeterminate composition was made in the following manner:

1200 grams of an aromatic petroleum fraction obtained by solvent-extraction of petroleum was reacted with 222 grams of P285 for 4 hours at 220-230" C. and then steamblown for 3.5 hours at 210 C. The highly viscous organo-phosphorus acid thus prepared was found to contain 4.35% phosphorus, 1.7% sulfur, and to have an acid number of 129.

287 grams (0.66 equivalent) of the above organophosphorus acid, 1110 grams (1 equivalent) of a 40% oil solution of barium petroleum sulfonate, 206 grams (1 equivalent) of diisobutyl-phenol (ratio of combined equivalents of phosphorus acid and sulfonate to diisobutyl-phenol is 1.66), 550 grams (7.2 equivalents) of B210, and 320 ml. of water were stirred for one hour at 100 C. Thereafter the process mass was elevated to 150 C. and treated with CO2 at that temperature until a substantially neutral titre was obtained on the process mass. After an additional hour of heating, the whole was filtered. The filtered product was viscous, brown, oilsoluble liquid having the following analyses:

A high molecular weight phosphorus acid of undetermined structure was prepared in the following manner:

3408 grams of polymerized isobutylene having an average molecular weight of about 750 were introduced into P25 and 84 grams of sulfur flowers was added slowly ver a period of about 1 /2 hours. After the addition had been completed the reaction mass was maintained at 2 05'2 l5 C. for an additional 2 /z hour period. The resulting mass was blown with steam for 2 hours at 20 5 2l-5 C. to remove some of the combined sulfur. The organo-phosphorus acid thus prepared contained 1.5% 4 PhQSPhQm n h an a i mber o 117.

240 grams (0.5 equivalent) of the above phosphorus sa d. .55 ms (9-5 equivalent) of a 0% o lut of barium'petroleum sulfonate, 124 gnams (0.6 equivalent) of diisobutylphenol (ratio of combined equivalents of phosphorus acid and sulfonate to diisobutylw phenol is 1.66), 340 grams (4.44 equivalents) of Rat), 300 ml, of water, and 565 grams of low-viscosity eral oil were stirred together for 1 hour at C. There: after the process mass was heated to C. over a 2 bee re ie nd hen bl w w h a u n f 02 un il the mass showed a substantially neutral titre (about 1 hour required). After heating for an additional halfl 9 Em -Vs S an a all of he a h process mass was filtered. The filtered product was a brown, oils s 1 9 3 a in t l w n a a y s:

rr:::';---:- Example 22 750 gnams (1 mole) of polymerized isobutylene having an average molecular weight of 750 were heated to 250 C. and treated with 510 grams (3 moles) of P861: over a 4.5 hour period. After all of the P361; had been added, the whole Was heated for 0.25 hour at 240 250 C. and a vacuum applied to remove volatile material. The residue was mixed with 375 grams of low viscosity mineral and blown with superheated steam for 1.5 hours at 150-175 C. Thereafter the material was diluted with a volume lactol spirits (a commercial hydrocarbon solvent), filtered, and subjected to distillation to remove the solvent. The organo-phosphorus acid of indetermi= nate composition thus prepared was a viscous, brown liquid containing 1.87% sulfur, 5.2% phosphorus," and had an acid number of 84. Analysis also indicated the presence of carbon to phosphorus linkages.

240 grams (0.36 3 equivalent) of said phosphorus acid, 1110 grams (1.0 equivalent) of a 40% oil solution of barium petroleum sulfonate, 169 grams (0.82 equivalent) of diisobutylphenol (ratio of combined equivalents of phosphorus acid and sulfonate to diisobutyl-phenol is 1.66), 439 grams (5.73 equivalents) of Ba(),, and 320 ml. of water were stirred together for about one hour at 100 C. Thereafter the process mass was elevated to 150 and blown with a current of CO2 until the Whole showed a substantially neutral titre. After the carbonation was completed, the mass was heated for an additional hour at 150 C. and then filtered. The filtered product was a Example 23 l 1 9 ram f unsaturated paraffin wax and 240 grams V was a viscous, dark-brown,

V were added over a period of 4 hours a material.

19 A of P285 were reacted together for about 4 hours at 140 C. 1250 grams of this reaction product were added slowly toza hot (100 C.) solution of 352 grams of NaOH" in 1056 ml. of 'water and the whole was heated for 5 hoursat the reflux temperature. After the process mass had cooled, it was acidified with hydrochloric acid. The organic layer was extracted with a volume of benzene, washed with "water, and heated under reduced pressu re to remove the benzene solvent. The organo-phosphorus acid of undetermined composition thus obtained was a brown liquid having an acid number of 61 and containing 7.8% sulfur and 3.4% phosphorus. It was found to contain carbon to phosphorus linkages.

928 grams (0.361 equivalent) of said phosphorus acid, 928 grams of a 40% oil solution of a mixture of equal molecular parts of barium petroleum sulfonate and barium di-isododecyl benzene sulfonate, 144 grams (0.7 equivalent) of diisobutyl-phenol (ratio of combined equivalents of phosphorus [acid and sulfonates to diisobutyl-phenol is 1.66), 378 grams (4.94 equivalents) of BaO,-and 300 ml. of water were stirred together for 1 hour at 100 C. Thereafter the process mass was heated to 150 C. and blown with a current of CO2 until the mass showed a substantially neutral titre (about 2 hours required). After an additional hour of heating at 150 C., the process mass was filtered. The filtered product oil-soluble liquid having the f l w n a aly s:

Example 24 1430 grams (0.55 mole) of chlorinated polyisobutylene (prepared'by chlorinating polyisobutylene of 750 average molecular weight with chlorine gas at 20-30 C. until it combined with 6% chlorine) were mixed with 21.5 grams of Superfiltrol (an acid-activated clay) and heated to 170C. Thereupon, 185 grams (1.09 moles) of P8013 while the process mass was held at 170-200 C. After all of the PSCls had been added, the whole was heated for 15 minutes at 220-230 C. and a vacuumapplied to remove volatile The residue wasmixed with 215 grams of low viscosity mineral oil and steam-blown for 1.5 hours at 150'-'l85 -C. Thereafter the process mass was heated at 170-190 C. until substantially all of the water was 7 removed. The filtered product, a high molecular weight organophosphorus acid of undetermined structure, was a viscous, dark-brown oil having an acid number of 61 and containing 1.51% sulfur, 3.4% phosphorus, and 0.32% chlorine.

:I 452 grams (0.49 equivalent) of said phosphorus acid, .1273 grams (0.99 equivalent) of a 35% oil solution of barium petroleum sulfonate, 183 grams (0.892 equivalent) of diisobu-tylphenol, 483 grams (6.31 equivalents) of BaO, 242 ml. of water, and 885 grams of low viscosity mineraloiLwere heated together for one hour at 100 C. Thereafter the process mass was heated to 150 1 60 C. and blown with a current of CO2 until it gave a substantially fneut-ral titre (about 2 hours required). After the mass had been heated an additional hour it was fi'l-tered. The filtered product was an oily, dark-brown, oil-soluble liquid having the following analyses:

Percent sulfur 3 a 1.33 Percentphosphorus 0.37 Percentchlorine 0.25 Percentbarium 13.2 Percent sulfate ash (calculated) 22.4 Basic No 4.5 Metal ratio 4.43

20 Example 25 420 grams (0.54 mole) of chlorinated polyisobutylene containing about 6% chlorine and prepared in the manner set forth in Example 24. were mixed'with 34 grams (1.06 atoms) 'of' sulfur flowers and 26.5 gramsof Superfiltrol and heated to 150 C. 147 grams (1.06 moles) of PSClr' were added slowly to the process mass, maintaining the temperature between 150 and 190 C. 'After' all of the PSCla had been added, the whole was heated for 1.25 hours at 192215 C. and then stripped of volatile material at 170 C. and mm. Hg absolute pressure. 210 grams of low viscosity mineral oil were added and the mass was blown with steam for 1.5 hours at 150-190 C. and then heated at 190 C. under reduced'pressureto remove volatile material. The process mass was filtered, yielding a viscous, dark-brown, oily organo-phosphorus acid of undetermined structure which had an acid No. of 60 and contained 1.67% sulfur, 2.85% phosphorus, and 0.48% chlorine. The presence of carbon to phosphorus linkages was also established. l

422 grams (0.454 equivalent) of said phosphorus acid, 938 grams (0.73 equivalent) of a 35% oil solution of barium petroleum sulfonate, 147 grams (0.713 equivalent) of diisobutylphenol, 392 grams (5.12 equivalents) of BaO, and 196 ml. of water were mixed and heated for one hour at 100 C. Thereafter the process mass was heated to 150 C. and blown with a current of C02 for 2 hours, at the end of which time a substantially neutral titre was obtained on the mass. After the Wholehad been heated an addi-tion-alhour at 150 C. it was diluted with 728 grams of low viscosity/mineral oil and filtered. The filtered product was a somewhat viscous, dark-brown, oilsoluble liquid having the following analyses:

Percent sulfur 1.27 Percent phosphorus 0.41 Percent chlorine 0.22 Percent barium 13.3 Percent sulfate ash (calculated) 22.6 Basic No 6.6 Metal ratio Example 26 7' 1975 grams (2.63 moles) of polymerized isobutylene having an average molecularweight of about 750 were" thewhole was stirred for 3 hours at 50-60 C. There- 7 after the process. mass was washed with water and dried by heating to C. under reduced pressure. The

residue, 2. barium salt of a high molecular weight organophosphorus acid of undetermined structure, was a brown, oil-soluble, viscous liquid containing 2.83% sulfur, 2.4% phosphorus, and 4.8% barium. 'Analysis also established the presence of carbon to phosphorus linkages.

450 grams (0.317 equivalent) of said organophosphorus salt, 762 grams (0.593 equivalent) of a 35 oil solution of barium petroleum sulfonate, 113 grams (0.548 equivalent) of diisobutyl-phenol, 275 grams (3.59 equiva- 'lents) of BaO, and ml. of water were heated together for one hour at 90100 C. Thereafter the processmass I was heated to C. and blown with a current of CO2 until -a substantially neutral titre was obtained on the mass (about 2 hours required). After the whole had been heated an additional hour at 150 C. to drive off subst ntially all of any water present, it was filtered.

grams of low viscosity 21 The filtered product was an oily, dark-brown, oil-soluble liquid having the following analyses:

Example 155 grams (0.62 equivalent) of eicosyl phosphonic acid, prepared in the manner set forth in U. S. 2,587,340 and extracted with methanol to remove u IJCQnverted eicosane, were admixed with 1110 grams (1.0 equivalent) of a 40% oil solution of barium petroleum sulfonate, 203 grams (0.978 equivalent) of diisobutyl-phenol, 536 grams (7.01 equivalents) of BaO, and 320 ml. of water and heated for one hour at 90l00 Thereafter the process mass was heated to 150 160 C. and blown with a current of CO2 until a substantially neutral titre was observed on a sample of the mass (about 2 hours required). After the whole has been heated an additional hour at 150 C., it was filtered. The filtered product was a viscous, dark-brown, oil-soluble liquid having the following analyses:

Example 28 ram ,(-62mQ es) Q seq t deeaas (P le xa e l was eacted ith 3 ram 14 1 1 of P255 for5 hours at 100 C. and 5 hours at 14015.0 C. Sa eact on p du t a ad q wis *9 a uxi s l n o 3 2sram f a H in 1 l e i water n the whole was stirred for about 5 hours at 100 C. After the process mass had cooled, it was acidified with concentrated hydrochloric acid and extracted with a volume of benzene. The benzene extract was washed with water and then heated under reduced pressure to remove the benzene solvent. The organo-phosphorus acid of undetermined structure thus obtained was a brown, oily liquid having an acid number of 38' and containing 4.4% sulfur and 2.4% phosphorus. It was also established that the material contained carbon to phosphorus linkages.

360 grams (0.244 equivalent) of said organo-phosphorus acid, 610 grams (0.526 equivalent) of a 40% oil solution of barium petroleum sulfonate, 96 grams (0.464 equivalent) of diisobutyl-phenol, 251 grams (3.27 equivalents) of 13210, and 2-12 ml. of water were mixed and stirred for one hour at 90100 C. The temperature was then elevated to 150 C. and a current of CO2 was blown through the process mass for 2 hours. After an additional hour of heating at 150 C., the process mass was filtered. The filtered product was a brown, oilsoluble liquid having the following analyses:

Percent sulfur 2.34 Percent phosphorus 0.60 Percent barium 18.3 Percent sulfate ash (calculated) 31.2 Basic'No. 8.5 Metal ratio 4.73

Example 29 260 grams (0 .37 equivalent) of bis-(tri-tertiary-amylphenyl) dithiophosphinic acid, 1030 grams (0.887 equivalent) of a 40% oil solution of barium petroleum sulfonate, 156 grams (0.757 equivalent) of diisobutyl-phenol, 410 grams (5.35 equivalents) of R210, and 290 ml. of water were stirred together for one hour at 90100 C.

2.2 The m a u of h Process mass was elevated "to 15.0.-.16,0- Q. and a current of CO2 was admitted through the mass for 2 hours at said temperature. Thereafter, the whole was heated for an additional hour at 150 C; and filtered. The filtered product was a. viscous, dark.- brown, oil-soluble liquid having the following analyses:

Percent sulfur a I a 2.72 Percent phosphorus 0.60 Percent barium Q Q Percent sulfate ash (calculated) 35.3 Basic N0. V I '7 i I i 6.9 Metal ratio 4.7

Example 30 3480 grams of polymerized isobutylene having an average molecular weight of about 750 were heated to 210 C. and an intimate mixture of 672 grams of P285 and 84 grams of sulfur flowers was added thereto over a period of 1.75 hours. After all of the PaS mixture had been added, the whole was heated for 1.5 hours at 210 C., diluted with 2600 grams of low viscosity mineral oil, and blown with steam for 5' hours at 2102 1 5 C. The filtered material, a high molecular weight organephosphorus acid of undetermined structure, had an acid No. of 68 and contained 0.9% sulfur and 2.14% phosphorus. i

820 grams (1.0 equivalent) of this organo-phosphorus acid, 56 grams (1.5 equivalents) of Ca(OH)2 and 2.00 ml. of water were refluxed for 2 hours and then elevated to 150 C. to remove substantially all of the water (2 hours at 150 C. required). The filtered process mass comprises an oil solution of the calcium salt of the organephosphorus acid. w v

In a sep at vessel, 88 m -of w t r 475 gr s (4.8.8 equivalents) of phenol, and 90 grams (2.44 equivalents) of Ca(OH) 2 were refluxed for 2 hours. To this vessel were added 333 grams (0.5 equivalent) of the above-described calcium salt of organophosphorus acid and 525 grams (0.5 equivalent) of a 45% oil solution of calcium petroleum sulfonate (6.5% sulfate ash content). 1 The process mass was refluxed for 2 hours at 110 and then heated to C. where it was blown with (3G2 for one hour. The substantially neutral process'mas s was then heated to 200 C. under reduced pressure Phenol, freed from calcium phenate by the carbonation step, was recovered to the extent of 91% in thedistillate. The residue was diluted with 300 grams of low viscosity mineral oil and filtered. The filtrate, the desired endproduct, was a brown, oil-soluble liquid having the following analyses: i

741 grams (0.905 equivalent) of the organo-phosphorus acid described in Example 30, grams (1.35 equivalents) of wet, freshly precipitated Mg(OH)2 containing 24% magnesium, and 100 ml. of water were refluxed for 2 hours and then heated at 150 C. to remove substantially all of the water present (about 2 hours required). The filtered material comprises the magnesium salt of the organo-phosphorus acid. It was found to contain 1.9% magnesium, 0.93% sulfur, and 1.99% phosphorus.

In a separate vessel, 94.6 grams (7.88 equivalents) of magnesium turnings were reacted with anhydrous methanol (1.5 liters) at the reflux temperature to repare a methanol solution of magnesium methoxide. To this solution were added 953 grams (1.0 equivalent) of a 39% oil solution of magnesium petroleum sulfonate, 63-2 r 23 grains (1.0 equivalent) of the above described'magnesium salt-f organo-phosphorus acid, and 248 grams (1.204 equivalents) of diisobu'tyl-phenoli. The whole'was stirred for 2 hours under reflux, then the methanol was dis- 7 tilled off. Thereafter, 80 ml. of water were added and Percent sulfur" 7 1.3 Percent phosphorus 0.40 Percent magnesium 3 75 Percent sulfate ash' (calculated) 18.6 Acid No. 15.5

Metal ratio" I Example 32 1764. grams of the organo-phosphorus acid described in Example 30, 110 grams (2.6 equivalents) of LiOH-HzO, and 300 ml. of Water were refluxed for 1.5 hours, then heated to 150 C. and held there for 1.5 hours to remove substantially all of the water. The process mass was filtered, yielding, as filtrate, the lithium salt of the organo-phosphorus acid. It was a brown liquid containing 1.0% sulfur, 2.3 phosphorus, and 0.96% lithium.

. In a separate vessel, 622 grams (1.0 equivalent) of a 60% oil solution of petroleum sulfonic acid, 600 grams of low viscosity mineral oil, 200 ml. of water, and 379 grams (8.99 equivalents) of LiOH-HzO were warmed to 70 C. and mixed'with 754 grams (1.0 equivalent) of the'above-described lithium salt of organo-phosphorus acid and 248 grams 1.204 equivalents) of diisobutylphenol. The process mass was refluxed for 2 hours and then heated at 150 C. for 2 hours. A current of CO2 was blown through the mass for 1 hour at 150 C., rendering it substantially neutral to titre. After the mass had heated an additional half-hour at 150 C., it was filtered.

' The filtered product was a brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.77 Percent phosphorus 0.74 Percent lithiur'n' 2.34 Percent sulfate ash (calculated) 18.5 Basic No. 5.7

Metal ratio 7 7 Example 33 a 738 grams of the organo-phosphorus acid described in Example 30, 902 grams of low viscosity mineral oil, and 800 ml. of water were stirred at 70 C. Then '111 grams (3.0 equivalents) of Ca(OH)2 were added and the masswas refluxed for 0.5 hour. Thereafter, 185 grams (5.0 equivalents) of Ca(OH)2, 1050 grams 1.0 equivalent) of a 45% oil solution of calcium petroleum. sulfonate, and 1315 grams (14.0 equivalents) of phenol were added and the process mass was refluxed for 3 hours. Substantially all of the water was removed by heating to 150 C., at which temperature CO2 was blown through the mass for 2 hours to render it substantially neutral on titre. A vacuum'was then applied and the temperature of the mass was raised to 200 C. to remove substantially all of the originalphenol used. The phenol was liberated from the calcium phenate in the process mass by the carbonation step.

2'4 7 Example 34 The experiment described in Example 33, was repeated using 590 grams (1.0equivalent) of a oil solution of di-isododecyl benzene sulfonic acid in lieu of the 1.0

' equivalent of calcium petroleum sulfonate specified therein. The filtered end-product in this instance was a brown, 7 oil-soluble liquid having the following analyses:

Percent sulfur V 1.08 Percent phosphorus 0.49 Percent calcium 4.1 Percent sulfate ash (calculated) 14.0 Basic No. 11.5 Metal ratio 2.96

Example 35 457 grams of the organo-phosphorus acid described in Example 30, 660 grams (0.467 equivalent) of a 30% oil solution of equal molecular proportions barium petroleum sulfonate (i. e., mahogany sulfonate) and barium white oil sulfonate (prepared from white oil sulfonic acid, which in turn was made by the well-known Reed process), 116 grams (0.562 equivalent) of diisobutyl-phenol, 318 grams (4.14 equivalents) of BaO, and

Percent sulfur 1.16 Percent phosphorus 0.42 Percent barium 13.84 Percent sulfate-ash (calculated) 23.5 Basic No. 8.3 Metal ratio 4.66

Example 36 565 grams (2 moles) of eicosane were heated to 194 C. and 169.3 grams (1 mole) of PSCla were added there- After substantially all of the phenol had been removed,

the residue was filtered. The filtered end-product was a brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.32 Percent phosphorus 0.47 Percent calcium 4.47 Percent sulfate ash (calculated) 15.2 Basic No. 11.5 iMetal ratio 3.22

to slowly beneath the surface over a 2 hour period at l94220 C. The temperature was then elevated over a 6 hour period to 254 C., whereupon a vacuum was applied to remove volatile material. The residue was steam-blown for 2 hours at 200 C., yielding a brown, waxy solid whose analysis corresponding approximately to di-eicosyl phosphinic acid.

238 grams (0.365 equivalent) of said organo-phos phorus acid, 724 grams (0.624'equivalent) of barium petroleum sulfonate, 123 grams (0.596 equivalent) of 'diisobutyl-phenol, 326 grams (4.26 equivalents) of BaO, and 222 ml. of water were stirredtogether for one hour at 100 C. The temperature of the process mass was then elevated to 150 C. and a current of CO2 was blown through the mass at 150. C. for 2 hours to render it substantially neutral on titre. Thereafter, the whole was heated an additional hour at 150 C. and filtered. The filtered end-product was a somewhat viscous, oilsoluble, dark-brown liquid having the following analyses:

Example 37 1110 grams (1.0 equivalent) of a 40% oil solution of barium petroleum sulfonate, grams (0.35 equivalent) of di-(2-ethyl-hexyl) phosphoric acid, 168grams (0.813 equivalent) of diisobutyl-phenol, 434 grams (5.67 equiv,- alents) of BaO, and 280 ml. of water were stirred toga her for 2 hours at 110 C. The temperature .of the mass was elevated to 150 C. and a current of CO2 was blown through the mass for 1.5 hours. Thereafter, the whole was heated for an additional 0.5 hour at 150 C. to remove substantially all of any water still remaining and then filtered. The filtered end'product was a viscous, dark-brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.64 Percent phosphorus 0.54 Percent barium 21.6 Percent sulfate ash (calculated) 36.7 Basic No. 12.2

Example 38 945 grams of the barium salt of the organo-phosphorus acid described in Example 30,713 grams (0.6 equivalent) of a 37% oil solution of barium di-isododecyl benzene sulfonate, 149 grams (0.723 equivalent) of diisobutylphenol, 362 grams (4.73 equivalents) of BaO, and 300 ml. of water were stirred together for 1 hour at 100110 C. The temperature of the process mass was then elevated to 150 C. and CO2 was blown through the mass for 1 hour to render it substantially neutral on titre. Thereafter, the process mass was heated for an additional 0.5 hour at 150 C. and filtered. The filtered end-product was a brown, oil-soluble liquid having the following analyses;

Example 39 500 grams of the potassium salt of the organop o uho us, a id des rib d n Examp 470 ram (0.424 equivalent) of 40% oil solution of barium petroleum sulfonate, 105 grams (0.51 equivalent) of diisobntyl-phenol, 288 grams (3.76 equivalents) of Bat), and 10,0 of water were heated together for one hour at 100l10 C. The temperature of the process mass was then raised to 150 C. and CO; was blown through the mass for one hour to render it substantially neutral on titre. Thereafter the Whole was heated an additional 0.5 hour to remove substantially all of any water present and then filtered. The filtered end-product was a brown, oilsoluble liquid having the following analyses:

Example 40 4 26 grams (3 moles) of alpha-methyl naphthalene were heated to 176 C. and 510 grams (3 moles of PSCls were added slowly thereto over an 8 hour period at 186 2l4 C. The temperature was then elevated to 263 C. and a vacuum applied to remove volatile material. The residue was steam-blown for one hour at 160185 C. and then dried by heating at 180 C. under reduced pressure. The residue, at high molecular Weight organo-phosphorus acid of undetermined structure, was a brittle solid having an acid number of 290 and containing 4.14% sulfur and 13.9% phosphorus. Analysis also established the presence of carbon to phosphorus linkages.

50 gran-is (0.259. equivalent).of said organo:plzlosphorusacid, 731 grams (0.568 equivalent). of a 35 oil solution of a mixture of equal molecular parts of barium .di? isododecyl benzene sulfonate and barium petroleum sulfonate, 102 grams (0.498 equivalent) of diisobutylphenol, 270 grams (3.52 equivalents.) of BaO, 689 grams of low viscosity mineral oil, and ml. of Water were stirred at the reflux temperature for one hour. The ternperature of the process mass was then elevated to C. and CO2 was blown through the mass for 2 hours to render it substantially neutral on titre. Thereafter the whole was heated an additional hour at 150 C, and filtered. The filtered end-product was a somewhat viscous, dark-brown, oil-soluble liquid having the following analyses:

Example 41 510 grams (3 moles) of vdiphenyl ether and 10 grams of Zinc chloride were heated to 190 C. and 510 grams ('3 moles) of PSC13 were added thereto slowly over a period of 10.5 hours at 19.0265 .C. Thereafter, volatile material was removed at 210 C. and 2.5 mm. Hg absolute pressure. The residue was steam-blown at 180 C. and when it became highly viscous, 300 ml. of ethanol, 250 ml. of water, and 600 ml. of xylene were added. The process mass was then refluxed for 2 hours. The organic layer was separated and the solvents re.- moved by heating to 160- C. under reduced pressure. The residue, a high molecular weight organo-phosphorus acid of undetermined structure, was a brittle solid having an acid number of 108.

75 grams (0.145 equivalent) of said acid, 835 grams (0.65 equivalent) of a 35% oil solution of barium petroleum sulfonate, 99 grams (0.478 equivalent) of diisobutylphenol, 251 grams (3.2.8 equivalents) of BaO, 502 grams of low viscosity mineral oil, and 13.0 ml. of water were stirred together for one hour at the reflux temperature. The temperature of the process mass was then elevated to 150 C. and CO2. wasv blown. through the mass for 2 hours. Thereafter, the whole was treated for an additional hour at 150 C. and filtered. The filtered endproduct was a somewhat viscous, dark-brown, oil-soluble liquid having the following analyses:

1800 grams (2 moles) of wax-substituted naphthalene were reacted with 111 grams (0.5 mole) of P255 for 5 hours at 22 The esu t n mate ia w s e e at 1 and St aml w r 2 hpur er e t water was removed by heating to 140 C. under reduced pressure, leaving an oily, brown liquid organo-phosphorus acid having an acid No. of 48 and containing 1.18% sulfur and 1.54% phosphorus. Analysis also established the presence of carbon tophosphorus linkages.

575 grams (0.382 equivalent) of the barium salt of said organo-phosphorus acid (prepared by reacting the acid with BaO at 70l10 C.), 278 grams (0.24 equivalent) of a 40% oil solution of barium petroleum sulfonate, 77 grams (0.375 equivalent) of diisobutyl-phenol, 188 grams (2.45 equivalents) of BaO, 95 ml. of Water, and 258 grams of low viscosity mineral oil were heated for one hour at 90-100 C. The temperature of the process 7 Percent sulfur Percent phosphorus 0.48

Percent barium 14.3

Percent sulfate ash (calculated) 24.3

Basic No 2 5.9

Metal ratio 4.81

Example 43 678 grams (3.0 moles) of isononyl-phenol were heated to 180 C. and 510 grams (3.0 moles) of PSCls were added thereto over a period of 10 hours at l80248 C. After the process mass had been stripped of volatile material at 180 C. under reduced pressure, it was steamblown for one hour at 160-20 5 C. and then dried at 185 'C and 40 mm. Hg absolute pressure. The residue (821 grams) was diluted with 450 grams of low viscosity mineral oil and filtered, yielding, as filtrate, a viscous, red-brown organo-phosphorus acid of undetermined composition having an acid number of 68.

250 grams (0.495 equivalent) of said acid, 1021 grams (0.794 equivalent) of a 35% oil solution of a mixture of equal molecular parts of barium di-isododecyl' benzene sulfonate and barium petroleum sulfonate, 160 grams (0.776 equivalent) of diisobutyl-phenol, 426 grams (5.56 equivalents) of BaO, 997 grams of low viscosity mineral oil, and 215 ml. of water were stirred together for one hour at 90100 C. The temperature of the process mass was then elevated to 150 C. and CO2 was blown through the mass for 2 hours at 150 C. to'render it substantially neutral on titre. Thereafter the whole was heated an additional hour at 150 C. and filtered. The filtered end-product was a dark-brown, oil soluble liquid having the following analyses:

Percent sulfur 1.13 Percent phosphorus 0.13 Percent barium 10.9 Percent sulfate ash (calculated) 18.5 Basic No 9.0 Metal ratio 3.6 5

Example 44 The experiment described in Example 35 was repeated using 658 grams (0.45 equivalent) of barium white oil sulfonate in lieu of the'0.467 equivalent'of mixed sulfonates specified therein. The end-product in this instance was a dark-brown, oil-soluble liquid having the following analyses:

Percent sulfur 1.03 Percent phosphorus 0.39 Percent barium- V 13.0 Percent sulfate ash (calculated) 22.1 Basic No p 6.4

Metal ratio 7 Example 45 heated an additional hour at 150 G and filtered. The

filtered end-product was a dark brown, oil soluble liquid having the following analyses: 1

Percent sulfur 1.81 Percent phosphorus 0.084 Percent barium 17.4 Percent sulfate ash (calculated) 29.6 Basic No I 7.1 Metal ratio 4.61

Example 46 640 grams (2.0 moles) of chlorinated paraflin wax containing 12% chlorine were heated to 215 C. and 340 grams (2.0 moles) of PSCla were added thereto over a 7-hour period at 215-180 C. (temperature dropped on continued addition); 12 grams of dry, acid-activated clay (Superfiltrol) were added and the whole was raised to 230 C. and held there for 3 hours, removing some unreacted PSCla by distillation as the reaction progressed. The temperature of the process mass was elevated to 250 C. and a vacuum was applied to draw off any re-, maining PSCla.

' 1.5 hours at 130155 C. and dried to 180 C. and

mm, Hg absolute pressure. The residue, a dark brown, liquid organo-phosphorus acid of undetermined structure, had an acid number of 101 and contained 5.3% sulfur, 6.64% phosphorus, and 2.96% chlorine.

180 grams (0.324 equivalent) of said acid, 1160 grams (1.0 equivalent) of a 40% oil solution of barium petro: leum sulfonate, 165 grams (0.8 equivalent) of diisobutyl-phenol, 425 grams (5.55 equivalents) of BaO, and 300 ml. of Water were refluxed for one hour at 90100 C. The temperature of the process mass was then elevated to C. and CO2 was blown through it for 2 hours to render it substantially neutral. Thereafter, the process mass was heated for an additional hour at 150 C. and filtered. The filtered end-product was' a viscous, dark-brown, oil-soluble liquid having the following analyses:

Percent sulfur V 2.17 Percent phosphorus 0.57 Percent chlorine 0.35 Percent barium V 20.4 Percent sulfate ash (calculated) 34.6 Basic No 8.9 Metal ratio 4.55

Example 47 Example 48 A product similar to that shown in Example 35 may be prepared by using 0.467 equivalent of petroleum sulfinic acid in lieu .of the 0.467 equivalent of mixed sulfonates specified therein.

Petroleum .sulfinic acid may be prepared conveniently by the reduction at 50. C..-60 C. of petroleum sulfonyl chloride with 25% aqueous sodium sulfite in the presence of suflicient NaOH (added dropwise) to keep the pH of the processmass around 8.0. The sodium salt is thereby obtained whichyields the acid on acidification with HCl,

The residue was then steam-blown for Example 49 A product similar to that shown in Example 35 may be prepared by using 0.467 equivalent of lauryl-phenyl sulfenic acid in lieu of the 0.467 equivalent of mixed sulfonates specified therein.

Example 50 A product similar to that shown in Example 35 may be prepared by using 0.562 equivalent of tetralin sulfonic acid as a promoter in lieu of the 0.5.62 equivalent of diisobutyl-phenol specified therein.

Example 51 A product similar to that shown in Example 35 may be prepared by using 0.562 equivalent of acetyl-acetone as a promoter in lieu of the 0.562 equivalent of diisobutylphenol specified therein.

Example 52 A product similar to that shown in Example 35 may be prepared by using 0.562 equivalent of di-isopropyl dithiophosphoric acid as a promoter in lieu of the 0.562 equivalent of diisobutyl-phenol specified therein.

The salt complexes produced in accordance with the present invention can be employed in lubricants including oils and greases, and for such purposes as in crankcases, transmission, gears, etc. as well as in torque converter oils. Other suitable uses for such complexes are in asphalt emulsions, insecticidal compositions, fire-proofing and stabilizing agents in plasticizers and plastics, paint driers, rust inhibiting compositions, pesticides, foaming compositions, cutting oils, metal-drawing compositions, flushing oils, textile treatment compositions, tanning assistants, metal cleaning compositions, emulsifying agents, antiseptic cleansing compositions, penetrating agents, gum solvent compositions, fat splitting agents, bonding agent for ceramics and asbestos, asphalt improving agents, flotation agents, improving agents for hydrocarbon fuels such as e. g., gasoline and fuel oil, etc.

More particularly, the complexes of this invention are especially adapted for the preparation of lubricants, paint driers and plastics, particularly the halogen bearing plastics. In these respects, the salt complex can be employed in the following concentrations based upon the weight of the total composition.

Broad Usual Preferred n Ra e. a percent percent percent Lubricant 0. 01-20 0. 2-15 0. 5l0 Stabilizing Agent for Plastics 0. 05- 5 0. 1- 3 0. 2 2 Paint Drier 2 25 0. 5-20 1. 0-15 LUBRICANT CONTAINING ORGANIC METAL COMPLEXES used with the products of the hereindescribed process to provide satisfactory lubricants may be found in S. Patent 2,723,234, column 36, line 25 through column 44, line 20.

As a consequence of a large number of tests performed on lubricants'containing metal complexes of our invention, we have been able to determine the operable rangee 9f m ta content and meta Su fa e ashsmltnt ($114919 th presence of our complexes) for both lubricant improving ents and fini hed lubricants- RANGES non WEIGHT PERCEN'L 0F METAL SULEATE ASH AVND METrLL (DUE To, METAL COMPLEX) IN LUBRICANT IMPROVING AGENTS AND LUBRICANTS Range broad, intermediate, preferred, percent percent percent In lubricant improving agent:

metal sulfate ash due' to v 0.38 to 40 0.64 to 30 1.28 to 20 metal complex. metlal due to metal com- 0.07 to 23.5 0.13 to 17.5 0.27 to 12 1.) ex. In lubricant:

metal sulfate ash due, to 0.002 to 8 0.005 to 6 0.01 to} metal complex. metial due to metal com- 0001 to 5 0.0011 to 3.5 0.02 to 2.5

p ex.

D e e e i e pl e hea dem nds n. e d e ge q c an Pr r es 9 a lubrican nd hes ema d be am p os' s l e e t as t e su fur co e t of e ue cr ases.- Since a ub nt al rq n of the d es fuels available to operators of diesel engines contain from 0.3 to 1% or more of sulfur in the form of naturallyoccurring sulfur compounds, it is important to provide lubricants which will counter ct the deleterious effect of such sulfur and maintain the engine in good mechanical condition by reducing the build-up of harmful deposits.

Ivietal complexes produced according to the teaching set forth in the instant application from'a mixture of both (a); at least one sulfur acid or salt thereof, and (b) at least one phosphorus acid or salt thereof, have been found to be of particular utility in preparing improved lubricants for use. in diesel engines, especially where such engines are operated on high sulfur content fuels,

In the diesel engine tests given hereinafter, certain additional improving agents of the oxidation and corrosion inhibition type were used in combination with the several metal complexes. For convenience, these havebeen designated as improving agents A and B. Their; composition is as follows:

A.P roduct prepared by reacting 4 moles of turpentine with 1 mole of PzS5 for about 4 hours at about C. B-A mixture of .40 mole-percent of zincdiisopropyl dithiophosphate with 60 mole-percent of zinc di-(4- methyl-sec-arnyl) dithiophosphate.

In any given group of tests wherein two metal complexes are directly compared, it will be noted that each is present n n mount th t mpa ts the same weight-nercent of metal sulfate ash, (and thus the same weight-percent of metal) to the lubricant. Since metal complexes of the instant application may vary considerably in metal content (and therefore metal sulfate ash content) valid test comparisons require that such metal complexes be compared when present on an equal weight-percent of metal sulfate ash in the lubricants.

I. Buda diesel engine test.-The diesel engine employed in this test is a single-cylinder, liquid-cooled engine which develops 7.5 brake-horsepowerat 1800 R. P. M. It is manufactured by the Buda Company of Harvey, Illinois, and bears the designation Model 1BD 38.

V 1 100=perfeetly clean. I In -perfectly clean.

adhered to in testing lubricants in the Buda engine: w V

III. Caterpillar diesel engine test of 120 hours duration. This test is similar to that set forth in section II flowing, oil-soluble liquid having the following analyses:

Basic No. 5.05 Percent sulphate ash 26.0 Metal ratio 4.52

forth in 'U. S. Army Ordnance Tentative Specification AXS-1551.

Merit rating for carbonaceous deposits in top ring .groove 2 Composition in SAE 30 solvent-extracted Alberta field motor oil (values are in weight-percent of the total lubricant) Merit rating for lacquer in lands 1 Overall merit rating for piston 1 Merit rating for lacquer in grooves Lube No.

0.5% sulfate ash as 97.2 9.3 V 10 10 barium complex prepared from a mixture of barium sulfonate and barium salt of a phosphorus acid of intermediate composition (Ex.

2)0.45% improving agent B.

0.5% sulfate ash as barium sulionate complex (Same as in Lubricant No. 2 above) 0.45% improving agent 13.

100 hours. above, except that the fuel employed had a sulfur content j gg g g fg of 1.0%. The heightened sulfur content of the fuel in- Fuel Diesel fuel oil containing about 0.4% 5 creases the severity of the test.

naturally occurring sulfur. Fuel consumption 3.05 lbs. per hour. Lublrlcant temperature- 175: F. 7 C00 ant temperature. 200 F. Test Result '1 t3 1,, Composition in es 8 10 SAE 30 solvent- 7 Merit extracted Midrating Merit Merit Composition i sAE 30 l t M t Lube Continent motor Overall for carrating 7 rating Lubricant refined Mid-Gontinentmotor oil rating N Oil (Values are in merit bOIlao o No. (values are inwelght-percent of Overall for care -pe of rating ceous lacquer q e the total lubricants) merit rating bonaceous the total lubri" f deposits in in for piston 1 deposits cant) piston l in top grooves 2 lands 2 in top ring ring groove 1 groove 1 'l 0.71% sulfate ash as barium sulfo- 74.1 5. 9 5 0 s e as s 7- 9. 10 10 nate-dithiophosphate (Ex. 1) barium complex I 0.13%improvlngagentA-0.46% prepared from a. improving agent B. mixture of barlum 2 0.71% sulfate ash as barium sulfo- 61.2 4.6 salt of p o nate complex (see below for de- D110l'11S a01d 0 tails of preparation)0.13% imdeterminate comproving agent A0.46%improvp n ing agent B. 0.54% lmprovmg 6 oiii u irt h 89 o 9 6 s 5 7 5 S a BS 3. 1 100=perfectly clean. B 10=periectly clean. 81 111111 siilfonat: The following 18 the details of preparation of the 9mplex.(same as n Lubricant No. barium sulphonate complex present in lubricant N0. 2 of 2 above)-0.54% the previous table. 7 r lfinprwmg agent 1700 grams of a oil solution of barium petroleum sulphonate (7.6% sulphate ash content) were admixed with 134 grams of diisobutyl-phenol (ratio of equivalents 1 100=periectly clean. of sulphonate to diisobutyl-phenol is 1.7). The mass 21=perfefly clean 7 was heated to 70 C. and 800 ml. of Water and 302 grams of'barium oxide were added. 'After the reaction mass has SPECIFIC EXAMPLES OF LUBRICANT IMPROV- been refluxed for one hour, the temperature was raised to ING AGENTS AND LUBRICANTS PREPARED 150 and held there f one houL USING THE METAL COMPLEXES OF THE Carbon dioxide was then passed through the mass for PRESENT INVENTION 38 minutesat a rate of 1,650. ml. per minute. Thereafter g V I the contents of the reaction vessel were filtered to sep- Qertalfl 0}1-S011lb1e PhosPholous'alld'sulliuf-bearlllg arate the sulphonate complex, which was brown, free- 40 gamc materlals used In y of the lubrlcant p tions illustrated herein are designated as follows (unless Improving Description Agent product prepared by reacting about 4 moles of turpentine with about 1 mole of Pass for about 4 hours at 140 0.; 61% solution in low viscosity mineral oil. 7 zinc di-(4-methyl-sec-amyl) dithiophosphate; 44% solution in low viscosity mineral oil. a 7 mixture of mole-percent zinc di-(4-methyl-sec-amyl) dithiophosphate and 40 mole-percent zinc di-isopropyl dithiophosphate; 40% solution in low viscosity mineral oil. barium salt of the mixed dithiophosphate diesters'obtained by treating a mixture of 4-methyl-see-amyl, n-hexyl, and capryl alcohols (3,2, and 3 parts by weight, respectively) with P 85; 39% solution in low-viscosity mineral oil.

' ing agent can be discerned by considering the weight percentages of the separate improving agents as parts by weight. For example, the lubricant improving agent corresponding to lubricant No. 7 would consists of 1 part by weight of improving agent B, plus 5 parts by weight of the complex of Example 17 (or 1.75 sulfate ash parts by weight thereof). If the separate improving agents do not themselves contain a proportion of mineral oil, some may be added, if necessary, to secure a fully liquid, multicomponent concentrate as discussed earlier in the section regarding improving agent concentrates.

The values in parentheses in the percent column below give the percent of metal sulfate ash percent in complex employed therein.

Composition (weight percent) Composition (weight percent) Lubricant Lubricant Number Number Percent component Percent component 5 94. SAE 30 mineral oil. 96. SAE 20 mineral oil. 7 5. 0 (1. 75) metal complex of Example 17. 29 1. 0 (0. 34) metal complex of Example 39.

1. 0 ismgfioving agenlt 2.2 55) megilltciimplex ft'ditlgamplle 3% t 90.0 30 minera o 0 co 3 i-capry i iop osp a e. 8 8. 0 (2. 82) metal complex of Example 18. 97. 5 SAE 20 mineral oil.

2. 0 improving agent 0. 30 2. 0 (0. 48) metal complex of Example 40. 92.52 SAE 30 mineral oil. 5 P and S bearing product of Example 79.

5. 3 (1. 8) metal complex of Example 19. 97. 3 SAE 30 mineral oil. 9 0. 2g improving agent; 31 g (0. 35) metal complex oigxample 41.

0.9 improving agen improving agen 0. 92 improving agent D. 93. 3 SAE 30 mineral oil. 93. 84 SAE 30 mineral oil. 32 6.0 (1.32) metal complex of Example 44.

3. 98(1. 46) metal complex of Example 20. 0. 5 nickel di-octadecyl dithiophosphate. 10 0.28 improving agent (3.; 1S 211E113 5 bearing piioduct of Example 60.

0.98 improving agent 9 minera oi. 0. 92 improving agent D. 33 3. 0 (1. 49) metal complex oi Example 5. 97. 13 SAE 30 mineral oil. 0.5 tri-(terrrbutyl-phenyl) dithiophosphate. 1. 47 (0. 39) metal complex of Example 21. 0. 3 P and S bearing product of Example 65. 11 0.25 improving ageng 4 9%.(5) (2 45) 811513130 minleral 1 9 1.15 improving agen 3 me comp exo xamp e 96. 83 SAE 30 mineral oil. 0.5 P and S bearing product of Example 80. 12 1. 65(0. 57) metal complex oi Example 22. 95. SAE mineral oil.

0. is improving agent; go (1. 75) metal complex ozfAExample 11. 0. improving agen .75 improving agen 0. 44 improving agent D. 98.3 SAE 30 mineral oil. 92. 00 SAE 30 mineral oil. 36 0. 2 (0. 052) metal complex oi Example 12. 5. 83(1. 98) metal complex rziilxarnple 23. istilxtgoa%ing flgagllt 13 0. 2 improving agen miner 0' O. 98 improving agent 13. 25 15. 0 (4. 6) metal complex of Example 15. 0.92 improving agent D. 37 2.0 zinc di-(methyl-cyclohexyl) dithiophos- 93. 94 SAE 30 mineral oil. phate.

3. 88(0. 86) metal complex of Example 24. 2. 0 P and S bearing product of Example 69. 14 0. 28 improving agent A.

0.98 improving agent B. 0. 92 improving agent D. i 2 parts per million. 94. 32 SAE 30 mineral oil. 4 I

5% 62) n gg 3 253335 g 30 Other modes of applying the principle of the invention 15 2 improviingggent p may be employed, change being made as regards the 0x83 improving agent dctails described, provided the features stated in any of 0.44 improvmg agent D. H h f 5,3 SAE 30 tmmerai {3,7 d the 1f0 owing claims, or t c equivalent 0 such, be

7 prior ar viscosi in ex improver. emp d 1. '8 0.38 metal com lex of Exam le 26. 16 8%; limprovnglzgeng p 35 We therefore particularly point out and distinctly claim lmpmvmg as our invention: 0.44 im rovinga entD. 9 5 33 Sign zo m ngral d 1. A process which comprises preparing and mixing prior ar viscosi in ex improver. 17 1 75m 73) me t al complex of E me 27. a mass in which, at 50 C., at least 50% of the components 0.2 improving a eing are 111 the liquid state, and 1n which mass the active com- 0. 83 improving agen 44 improving age/MD poncnts consist of. 95. 35 (0 8) SA;E140 minleral p11. 1 28 1.85 .5 me a comp ex 0 Examp e 1s o. 14 improving agent A. A. Annxture of:

53 $58335 252%; g- (i) At least one oil-soluble organic acid compound 95. 05 SAE 40 mineral oil: having at least 12 carbon atoms in the molecule 9 120.11) riggazgi i rrgg gi p selected from the class consisting of aliphatic and 1.2 improving agent B. cyclic sulphur acids and the salts thereof; and,

gzg gfglgf g ggfg g: (ii) At least one oil-soluble organic acid compound 2.12(o.3) metal complex of Example 30. having at least 12 carbon atoms in the molecule 20 ggigzfig 322% g: selected from the class consisting of the aliphatic 2% iSuApEo:%ing agen1t P5 and cyclic phosphorus acids and the salts thereof;

. mmera 0 3.4 (0.63) metal complex of Example 31, the ratio of equivalents of (1) to (n) being from 0.10 to 21 x 0. 4g improving agent; l0;

1. 1 improving agen 9(I)44 gig???) anti toalmlzlagent.

4. minera o 338m 63) {metal c9mplex of Example 5 B. orgamc compound selected from the class con- 22 8%? p v n n: sisting of orgamc salt-forming compounds and the salts improving agen 0.92 im rovin a ent 1;. thereof, sa d orgamc compounds hav1ng g g-g (1 2 22 3 2 33 4 mp1 33 (1) An ionization constant in water of at least aoout D 8 23 o. 5 zinc di-ianry ditniopnos hete. X at about 2 9 g i g gegr g g c p 5 (n) A water solublhty at 50 C. of at least about 24 0 (0.84) metal complex of Example 34. "(10005 and g 5 3 2 g gg gggffgg gg gggfigfiff- (m) In saturated aqueous solutions at about 25 C.

84.0 sen 10 mineral oil. a pH of less than 7; 2 3% (3-5) 'gfgfg i iggigfigfifig the relative total amount of A and B used being in the gg gig-(12%bearinglprgductofExamplefio. range of from about one equivalent of the total amount of mmera 01 (L75) metal complex Example A to about 10 equivalents of B to about 10 equivalents 2e 1.5 0. 35) metal complex oi Example 35. of the total amount of A to about one equivalent of B;

0. 5 trilauryl tritlnopnosphate. l 0.3 gilnzdzg bearing pfioduct of Example 68.

95. mmera o 27 4.0 (1.43) metal complex of Example 37. C A paslcaliy rfaactmg metal compound I 0.8 calcium di-n-decyl dithiophosphate. (1) Which is water-soluble at a tem crature 0]. 50 2 P d S h d t f E l 6" p 85 f; 20 ggs 0 ramp 6 C. to the extent of at least about 0.0003 28 (0. 69) IIletElgl(E1mp1el0fhEXB-g1%lg 8. h h. t (ii) In an amount such that there are present in the zmc aury -p ny 10p osp ma e.

5 P and S bearing product of Example 76 mass substantially more than 1 equivalent of metal,

including the metal present in the remaining componcnts, per equivalent of A plus B; and

D. Water, in an amount equal to at least about one-tenth mole per mole of C; manama' tsgnags at; temperature and' for a period of time suficient to de i fi ub t ntial ll free ter nd.

water of hydration which may be present, and iform the organic metal complex.

2. The process of claim 1 further characterized'inthat' said process mass is treated prior to filtration with an acidic material of which the ionization constant is higher" than the ionization constant of the organic salt-forming compound of component B and in amounts suflicient' to" prepared by reacting an unsaturated compound with a phosphorus sulfide.

4. The process of claim 1 further characterized in that component A (ii) is at least one phosphorus acid compound prepared by reacting at least one unsaturated compound With a phosphorus sulfide and with sulfur.

5. The process of claim 1 further characterized in that component A(i) is at least one petroleum sulfonic acid and component A (ii) is at least one phosphorus acid having more than 12 carbon atoms. r

6. The process of claim 1 further characterized in that component A (i) is at least one mahogany sulfonic acid and component A (ii) is at least onephosphorus acid having more than 12 carbon atoms.

7.' The process of. claim 1 further characterized in that component A (i) is at least one alkyl benzene sulfonic acid and component A (ii) is at least one phosphorus acid having more than 12 carbon atoms.

8. The process of claim 1 further characterized in that component A (i) is at least one sulfur acid having more than 12 carbon atoms; component A (ii) is at least one phosphorus acid having more than 12 carbon atoms and component B is at least one phenolic compound.

9. The process of claim 1 further characterized in that component A (i) is at least one sulfur acid having more than 12 carbon atoms; component A (ii) is at least one phosphorus acid having more than 12 carbon atoms and component C is at least one basically-reacting metal com-" pound of which the metal is selected from the class con; 7

sisting of metals of group I havingaan atomic weight fless than 40 and themetals. of group II having an atomic weight less than 138.

10. The process of claim 1 further characterized in that 7 component A (i) is at least one sulfuracid having-more than 12 carbon atoms; component A (ii) is at least one phosphorus acid having more than '12 carbon atoms and component C is at least one l Jasically-reacting alkaline earth metal compound. W 1

11. The process of claim 1 further characterized in that component A (i) is at least one sulfur acid having more than 12 carbon atoms; component A (ii) is at least one phosphorus acid having more than 12 carbon atoms and component C is at least one basically-reacting barium compound. 3

12. The process of claim 1 further characterized in that component A (i) is at least one sulfur acid having more than 12 carbon atoms; component A (ii) is at least one phosphorus acid having more than 12 carbon atoms and in which the process mass is further treatedprior to filtration with CO2 inamounts sufiicient to liberate a substantial proportion of said organic compounds of componentR' 13. The processor claim 1 further characterized in that component A (i) is a mixture of petroleum mahogany sulfonic acid compounds and at least one alkyl aromatic sulfonic acid compound.

14. The product in accordance. with the process of 7 claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,418,894 McNab et a1. Apr. 15, 1947 2,491,649 Duncan et al Dec. 20, 1949 2,616,904 Asseff et al Nov. 4, 1952 2,616,905 Asseif et a1 Nov. 4, 1952 2,616,911 Assefi et a1 Nov. 4, 1952 2,616,924 Asseff et al. Nov. 4, 1952 2,616,925 Assefi et al Nov. 4, 1952 2,617,049 Assetf et al. Nov. 4, 1952 

1. A PROCESS WHICH COMPRISES PREPARING AND MIXING A MASS IN WHICH, AT 50* C., AT LEAST 50% OF THE COMPONENTS ARE IN THE LIQUID STATE, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST OF: 